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The structure and binding mode of citrate in the stabilization of gold nanoparticles

Nature Chemistry volume 9, pages 890–895 (2017)Cite this article

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Abstract

Elucidating the binding mode of carboxylate-containing ligands to gold nanoparticles (AuNPs) is crucial to understand their stabilizing role. A detailed picture of the three-dimensional structure and coordination modes of citrate, acetate, succinate and glutarate to AuNPs is obtained by 13C and 23Na solid-state NMR in combination with computational modelling and electron microscopy. The binding between the carboxylates and the AuNP surface is found to occur in three different modes. These three modes are simultaneously present at low citrate to gold ratios, while a monocarboxylate monodentate (1κO1) mode is favoured at high citrate:gold ratios. The surface AuNP atoms are found to be predominantly in the zero oxidation state after citrate coordination, although trace amounts of Auδ+ are observed. 23Na NMR experiments show that Na+ ions are present near the gold surface, indicating that carboxylate binding occurs as a 2e− L-type interaction for each oxygen atom involved. This approach has broad potential to probe the binding of a variety of ligands to metal nanoparticles.

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Figure 1: Gold nanoparticle diameter distributions and particle morphology.
Figure 2: 13C and 23Na nuclear magnetic resonance spectra and assignment of 13C NMR signals to citrate binding motifs.
Figure 3: DFT-optimized ligand geometries, binding energies and strain energies on Au(100) and Au(111) model surfaces.

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Acknowledgements

This work received support from the King Abdullah University of Science and Technology (KAUST) and ERC Advanced Grant No. 320860. For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science & Technology (KAUST) in Thuwal, Saudi Arabia.

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Authors and Affiliations

  1. Physical Sciences and Engineering Division (PSE), KAUST Catalysis Center (KCC), King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia

    Hind Al-Johani, Edy Abou-Hamad, Abdesslem Jedidi, Shiv Shankar Sangaru, Samy Ould-Chikh, Michael J. Kelly, Mohamad El Eter, Luigi Cavallo & Jean-Marie Basset

  2. Chemistry Department, University of Tabuk, College of AlWajh, Al Wajh, Saudi Arabia

    Hind Al-Johani

  3. Department of Chemistry, King Abdulaziz University, Jeddah, Saudi Arabia

    Abdesslem Jedidi

  4. Department of Chemistry, Durham University, Durham, DH1 3LE, UK

    Cory M. Widdifield

  5. Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland

    Jasmine Viger-Gravel & Lyndon Emsley

  6. Institut de Sciences Analytiques (CNRS/ENS de Lyon/UCB-Lyon 1), Centre de RMN a Tres Hauts Champs, Universite de Lyon, Villeurbanne, France

    David Gajan

  7. Imaging and Characterization Laboratory, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia

    Dalaver H. Anjum, Mohamed Nejib Hedhili & Andrei Gurinov

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  1. Hind Al-Johani
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Contributions

H.A.J. prepared the nanoparticles, and participated in analytical data collection and analysis; E.A.H. collected and analysed solid-state NMR data; A.J. carried out DFT calculations; C.M.W. carried out DFT calculations, analysed data from all techniques, and wrote the paper; J.V.G. recorded and analysed 23Na NMR data and wrote the paper; S.S.S. recorded XPS data; D.G. recorded and analysed low-temperature NMR data; D.H.A. and S.O.C. did the TEM measurements and analysis; M.N.H. recorded and analysed XPS data; A.G. acquired solid-state NMR data; M.J.K. acquired and analysed X-ray diffraction data; M.E.E. synthesized the AuNPs and coordinated their analysis; L.C. supervised and carried out DFT calculations, analysed the data and wrote the paper; L.E. conceived the study, supervised the solid-state NMR spectroscopy and chemical shift calculations, analysed the data and wrote the paper; J.M.B. conceived the study, supervised the preparation and analysis of the AuNPs, analysed the data and wrote the paper.

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Correspondence to Mohamad El Eter, Luigi Cavallo, Lyndon Emsley or Jean-Marie Basset.

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Al-Johani, H., Abou-Hamad, E., Jedidi, A. et al. The structure and binding mode of citrate in the stabilization of gold nanoparticles. Nature Chem 9, 890–895 (2017). https://doi.org/10.1038/nchem.2752

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